KR101432737B1 - Hybrid organic-inorganic thin film and producing method of the same - Google Patents

Abstract

The present invention relates to a method for producing an organic-inorganic hybrid thin film comprising interlayer-bonding an inorganic crosslinked layer and an organic polymer through molecular layer deposition (MLD), an organic-inorganic hybrid thin film prepared by the above- An organic electronic device including the organic-inorganic hybrid thin film, and a thin film transistor.

Description

TECHNICAL FIELD [0001] The present invention relates to an organic-inorganic hybrid thin film and a method for producing the organic-

The present invention relates to a method for producing an organic-inorganic hybrid thin film comprising interlayer-bonding an inorganic crosslinked layer and an organic polymer through molecular layer deposition (MLD), an organic-inorganic hybrid thin film prepared by the above- An organic electronic device including the organic-inorganic hybrid thin film, and a thin film transistor .

Many materials used in organic electronic devices are conjugated organic polymers having crossed double and single bond backbones through which electrons can flow. Due to their structural and variable electronic properties, conductive polymers are flexible and inexpensive and can be used in many applications such as flexible displays, radio frequency identification devices (RFIDs), smart cards, nonvolatile memories and sensors. . These polymers have one-dimensional properties, and the thin film of conjugated polymer has a disordered structure with each polymer strand twisted and bent. In most applications, attempts have been made to uniformly align polymer chains to control the efficiency with which light and electrons can be transported by polymer molecules. Korean Patent Registration No. 10-0957528 discloses a method for producing a crosslinked organic-inorganic hybrid composite using a small amount of inorganic oxide particles and a silicone-based crosslinked polymer precursor.

In order to solve the above problems, the present inventors have found that incorporation of a stable inorganic cross-linking layer into a conjugated organic polymer can better control the arrangement, stability and electronic properties of the organic polymer chain, thus completing the present invention.

The present invention relates to a method for producing an organic-inorganic hybrid thin film, which comprises interlayer-bonding an inorganic crosslinked layer and an organic polymer through molecular layer deposition (MLD), and a method for producing an organic- Thin film. Also, the present invention provides an organic electronic device and a thin film transistor including the organic-inorganic hybrid thin film.

However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.

The first aspect of the present invention provides a method for producing an organic-inorganic hybrid thin film, which comprises interlayer bonding an inorganic crosslinked layer and an organic polymer through molecular layer deposition (MLD).

The second aspect of the present invention provides an organic-inorganic hybrid thin film produced by the first aspect of the present invention.

The third aspect of the present invention provides an organic electronic device comprising the organic-inorganic hybrid thin film according to the second aspect of the present invention.

A fourth aspect of the invention is directed to a method of forming a substrate, A semiconductor channel comprising an organic-inorganic hybrid thin film according to the second aspect of the present invention formed on the substrate; And source / drain electrodes formed on the semiconductor channel.

The organic-inorganic hybrid thin film produced by the method for producing an organic-inorganic hybrid thin film, which comprises interlayer-bonding an inorganic crosslinking layer and an organic polymer through molecular layer deposition (MLD) of the present invention, And the conjugated organic polymer layer is bonded to form a two-dimensional organic-inorganic hybrid thin film. The inorganic layer of the organic-inorganic hybrid thin film of the present invention constitutes an extended structure bonded by a strong covalent bond, thereby imparting excellent thermal stability and mechanical stability as well as high carrier mobility. In addition, the molecular layer deposition (MLD) used herein enables precise control of film thickness at low temperatures, large uniformity, excellent conformality, excellent reproducibility and a sharp interface. The organic-inorganic hybrid thin films of the present invention exhibit excellent thermal stability and mechanical stability, and high field-effect mobility (> 1.3 cm ² V ^-1 s). The MLD method is an ideal technique for the production of various organic-inorganic hybrid thin films having an inorganic crosslinked layer, and is also applicable to the production of an organic polymer-inorganic hybrid superlattice.

FIG. 1 is a schematic view showing a process of interlayer bonding an inorganic crosslinked layer and an organic polymer by molecular layer deposition according to an embodiment of the present invention.
FIG. 2 is a schematic view illustrating a process of interlayer bonding an inorganic crosslinked layer and an organic polymer by a molecular layer deposition method according to an embodiment of the present invention.
FIG. 3 is a graph showing the thickness of a ZnOPDA film as a function (a) of a DEZ injection time and a function (b) of an HDD injection time in one embodiment of the present invention.
FIG. 4 shows a graph (b) and an AFM image (c) showing the relationship between the thickness of the ZnOPDA film and the number of MLD cycles in the TEM image (a) of the ZnOPDA film in one embodiment of the present invention.
FIG. 5 shows the Raman spectrum (a) and the XP spectrum (b) of the ZnOPDA film according to one embodiment of the present invention.
FIG. 6 shows the photoluminescence spectrum of a PDA film without ZnOPDA and inorganic cross-linking layer in one embodiment of the present invention.
7 is a cross-sectional view of a TFT having a ZnOPDA active layer on a highly-doped Si substrate, in one embodiment of the present invention.
8 is a graph showing the drain current-drain voltage ( I _D - V _D ) output curves of TFTs according to one embodiment of the present invention.
9 is a graph showing the drain current-gate voltage ( I _D - V _G ) transition curve and the gate leakage level of the TFT in one embodiment of the present invention.
10 shows an infrared spectral spectrum of a TiOPDA film and a precursor according to one embodiment of the present invention.
11 shows a UV-VIS spectroscopic spectrum of a TiOPDA film and a precursor according to one embodiment of the present application.
Figure 12 shows an XPS plot of a TiOPDA film, according to one embodiment of the invention.

Hereinafter, embodiments and examples of the present invention will be described in detail to enable those skilled in the art to easily carry out the present invention.

It should be understood, however, that the present invention may be embodied in many different forms and is not limited to the embodiments and examples described herein.

Throughout the specification, when an element is referred to as "comprising ", it means that it can include other elements as well, without excluding other elements unless specifically stated otherwise. As used herein, the terms "about," " substantially, "and the like are used herein to refer to or approximate the numerical value of manufacturing and material tolerances inherent in the stated sense, Accurate or absolute numbers are used to prevent unauthorized exploitation by unauthorized intruders of the mentioned disclosure. Also, throughout the present specification, the phrase " step "or" step "does not mean" step for.

Throughout this specification, when a member is "on " another member, it includes not only when the member is in contact with the other member, but also when there is another member between the two members.

The first aspect of the present invention provides a method for producing an organic-inorganic hybrid thin film, which comprises interlayer bonding an inorganic crosslinked layer and an organic polymer through molecular layer deposition (MLD).

According to one embodiment of the present invention, the method for producing an organic-inorganic hybrid thin film comprises: bonding an inorganic crosslinked layer on a substrate in an MLD chamber; And bonding the hexagonal diol (HDD) to the inorganic crosslinked layer bonded on the substrate But is not limited to, performing one or more process cycles including UV polymerization and polymerization.

The MLD is a gas-phase layer growth method similar to atomic layer deposition (ALD), in which an organic monolayer is formed in each order by sequential saturation surface reactions. In one embodiment herein, the MLD can be used to combine the inorganic bridging layer and the conjugated organic polymer layer to form 2D polydiacetylenes. The inorganic layer constitutes an extended structure bonded by a strong covalent bond, conferring high thermal stability and mechanical stability as well as high carrier mobility. The advantage of MLD technology is that it allows for precise control of film thickness at low temperatures, large uniformity, excellent conformality, excellent reproducibility, multilayer processing capability, sharp interfaces and excellent film quality at low temperatures. For example, a 2D polydiacetylene thin film is formed by a UV polymerization method in which a ligand-exchange reaction of an inorganic cross-linking layer and a hexadiyne diol (HDD) occurs, and OH groups at both ends of the diol are sequentially reacted with an inorganic cross- To produce a bridged alkane, so that monolayer precision can be achieved. The inorganic oxide cross-linked polydiacetylene thin films exhibit increased carrier mobility or other properties due to their 2D structure.

A method of manufacturing an organic-inorganic hybrid thin film according to an embodiment of the present invention will be described with reference to FIGS. 1 and 2. FIG.

FIG. 1 schematically shows a process for preparing a zinc oxide cross-linked polydiacetylene (ZnOPDA) thin film using diethylzincl DEZ as an inorganic cross-linking layer. In the MLD chamber, a DEZ molecule The substrate is exposed to form an ethyl zinc monolayer. The DEZ molecules are chemically adsorbed on the surface of the substrate rich in hydroxy groups through ligand-exchange reactions to form C ₂ H ₅ ZnO species. The ethyl group of the chemically adsorbed ethyl zinc molecule on the substrate is then displaced with the OH group of the HDD having living ethane to form a diacetylene layer and the OH group of the diacetylene layer is then transferred to the To provide the active site. The diacetylene molecules are then polymerized by UV irradiation to form a polydiacetylene layer. Zinc oxide cross-linked polyacetylene (ZnOPDA) thin films are sequentially grown under vacuum by adsorption of DEZ and HDD and UV polymerization. The expected monolayer thickness of the ideal model structure of ZnOPDA is about 6 Å, but is not limited thereto.

2 schematically shows a process for preparing a titanium oxide cross-linked polydiacetylene (TiOPDA) thin film using TiCl ₄ as an inorganic cross-linking layer, wherein the substrate is exposed to TiCl ₄ molecules in an MLD chamber Thereby forming a titanium dichloride monoxide layer. The TiCl ₄ molecule is adsorbed on the surface of the substrate rich in hydroxy groups through a ligand-exchange reaction. Then, the chlorine group of the titanium dichloride molecule chemically adsorbed on the substrate is substituted with the OH group of the HDD having living ethane to form a diacetylene layer, and the OH group of the diacetylene layer reacts with the exchange reaction of the next TiCl ₄ molecule Lt; / RTI > The diacetylene molecules are then polymerized by UV irradiation to form a polydiacetylene layer. Titanium oxide cross-linked polyacetylene (TiOPDA) thin films are sequentially grown under vacuum by adsorption of TiCl ₄ and HDD and UV polymerization.

According to one embodiment of the present invention, the organic polymer may be an initiator-free photopolymerizable polymer free from an initiator for initiating polymerization, and may be used without limitation, for example, polydiacetylene or vinyl ether But is not limited to, vinyl ether-aleimide.

According to one embodiment of the present invention, the inorganic cross-linked layer may include an oxide of a metal selected from the group consisting of Zn, Al, Ti, Zr, Sn, Mn, Fe, Ni, Mo, But is not limited thereto. The inorganic cross-linked layer forms a hybrid organic-inorganic structural material, allowing better control of the arrangement, stability, and electronic properties of the organic polymer chain. The organic-inorganic hybrid conductive polymer can be an ideal material for use in an organic electronic device, because the stable and excellent electrical properties of the inorganic component add to the structural flexibility and variable optoelectronic properties of the organic component.

According to one embodiment of the present invention, the organic-inorganic hybrid thin film may be two-dimensional, but is not limited thereto.

According to one embodiment of the present invention, the hexadienediol (HDD) may include a self-terminating reaction when bound to the inorganic crosslinked layer bonded on the substrate, It is not. In the MLD, in order to produce a uniform, conformal and high-quality poly-diacetylene thin film, it is preferable that the surface reaction of the HDD is self-terminating and complementary

According to one embodiment of the present disclosure, the inorganic crosslinking layer may be bonded on the substrate and then purged, but the present invention is not limited thereto.

According to one embodiment of the present disclosure, the inorganic crosslinked layer bonded on the substrate may further include, but is not limited to, bonding and then purging hexadienediol (HDD).

According to one embodiment of the present invention, purge gas may be purged using argon (Ar), nitrogen (N ₂ ), helium (He) or the like, but is not limited thereto.

The second aspect of the present invention provides an organic-inorganic hybrid thin film produced by the method for producing an organic-inorganic hybrid thin film of the first aspect of the present invention.

According to one embodiment of the present invention, the organic-inorganic hybrid thin film may be two-dimensional, but is not limited thereto.

The third aspect of the present invention provides an organic electronic device comprising the organic-inorganic hybrid thin film according to the second aspect of the present invention.

A fourth aspect of the invention is directed to a method of forming a substrate, A semiconductor channel comprising an organic-inorganic hybrid thin film according to the second aspect of the present invention formed on the substrate; And source / drain electrodes formed on the semiconductor channel.

According to one embodiment of the invention, the thin film transistor may have a field effect mobility of about 1.2 cm ² V ^-1 s to about 1.7 cm ² V ^-1 s, but is not limited thereto.

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited thereto.

[ Example ]

matter

All commercial materials, unless otherwise noted, are commercially available from Aldrich Chemical Co. And used without further purification. 2,4-Hexadiyne-1,6-diol (HDD) was purchased from Tokyo Chemical Industry. The deionized water was purified using a Millipore Milli Q Plus system, distilled on KMnO ₄ , and passed through a Millipore Simplicity system.

Example  One

Preparation of Substrate

The Si substrate was prepared by cutting a p-type (100) wafer (LG Siltron) having a resistivity in the range of 1-5 Ωm. A Si substrate, and Ishizaka Shiraki (A. Ishizaka, Y. Shiraki , J. Electrochem. Soc. 1986, 133, 666-671) with the chemical was treated by the cleaning process, the chemical cleaning process dressing, HNO ₃ proposed by (Alkaline treatment) in HNO ₃ / H ₂ O, heating with HCl (acid treatment), washing with deionized water and blowing with nitrogen-drying to remove contaminants and to grow a thin protective oxide layer on the surface .

Molecular layer  deposition

The oxidized Si (100) substrate was introduced into a Cyclic 4000 MLD system (Genitech, Taejon, Korea). A zinc oxide cross-linked polydiacetylene (ZnOPDA) thin film was deposited on the substrate using DEZ and HDD as precursors. Argon was supplied as both a carrier gas and a purge gas. DEZ and HDD were evaporated at 20 캜 and 80 캜, respectively. The cycle consisted of exposing to DEZ for 2 seconds, purging with Ar for 10 seconds, exposing to HDD for 10 seconds, and purging with Ar for 50 seconds. The total flow rate of Ar was 50 sccm. The deposited HDD layer was exposed to UV light (? = 254 nm, 100 W) for 30 seconds. The ZnOPDA film was grown at a temperature of about 100 DEG C to about 150 DEG C under a pressure of 300 mTorr.

Example  2

Preparation of Substrate

The Si substrate was prepared by cutting a p-type (100) wafer (LG Siltron) having a resistivity in the range of 1-5 Ωm. A Si substrate, and Ishizaka Shiraki (A. Ishizaka, Y. Shiraki , J. Electrochem. Soc. 1986, 133, 666-671) with the chemical was treated by the cleaning process, the chemical cleaning process dressing, HNO ₃ proposed by (Alkaline treatment) in HNO ₃ / H ₂ O, heating with HCl (acid treatment), washing with deionized water and blowing with nitrogen-drying to remove contaminants and to grow a thin protective oxide layer on the surface .

Molecular layer  deposition

The oxidized Si (100) substrate was introduced into a Cyclic 4000 MLD system (Genitech, Taejon, Korea). A zinc oxide cross-linked polydiacetylene (TiOPDA) thin film was deposited on the substrate using TiCl ₄ and HDD as precursors. Argon was supplied as both a carrier gas and a purge gas. TiCl ₄ and HDD were evaporated at 20 ° C and 80 ° C, respectively. The cycle consisted of exposing to TiCl ₄ for 2 seconds, purging with Ar for 10 seconds, exposing to HDD for 10 seconds and purging with Ar for 50 seconds. The total flow rate of Ar was 50 sccm. The deposited HDD layer was exposed to UV light (? = 254 nm, 100 W) for 30 seconds. The TiOPDA film was grown at a temperature of about 100 < 0 > C to about 150 < 0 > C under a pressure of 300 mTorr.

Experimental Example  One

Example  1 of ZnOPDA  Investigate the characteristics of the film

A Raman spectroscopy of the ZnOPDA film prepared as in Example 1 was obtained using a Raman spectroscopy system (Renishaw Model 2000) equipped with a built-in microscope (Olympus BH2-UMA). A 514.5 nm line from a 20 mW air-cooled Ar ⁺ laser (Melles-Griot Model 351 mA520) was used as the excitation source. Raman scattering was detected at 180 ° geometry using a Peltier-cooled (-70 ° C) charge-coupled device (CCD) camera. The Raman band of the silicon wafer at 520 cm <& quot ^{; 1} > was used to adjust the spectroscope. All XP spectra were recorded on a ThermoVG SIGMA PROBE spectrometer using an Al _Ka source operating at 15 kV and 70 W. The binding energy scale was adjusted to 285 eV at the major C 1s peak. Each sample was analyzed at < RTI ID = 0.0 > 90 < / RTI > The thickness of the polymer film was measured with an ellipsometer (AutoEL-II, Rudolph Research) and a transmission electron microscope (TEM: JEM2100F, JEOL). The current-voltage curve of the TFT was measured with a semiconductor parameter analyzer (HP4155C, Agilent Technologies). Optical properties were measured by photoluminescence (PL) spectroscopy using a He-Cd laser (325 nm) with a spectroscope (Darsa, PSI Co. Ltd.).

result

In an accurate MLD process, the surface reaction must be self-terminating and complementary in order to produce a uniform, conformal, and high-quality poly-diacetylene film. To verify that the surface response to the HDD is actually self-terminating, the dosing time is varied from 1 second to 20 seconds. The growth rate of the ZnO-PDA film was measured using an ellipsometer at growth temperatures ranging from about 100 캜 to 150 캜. The film thickness obtained per cycle for the HDD was saturated when the loading time exceeded 10 seconds (Fig. 3B). This result indicates that the HDD has undergone a self-closing reaction with DEZ adsorbed on the Si substrate. Figure 3A shows that the growth rate as a function of DEZ dosing time is saturated quickly when the pulse time exceeds 0.5 seconds. These results indicate that DEZ has undergone a rapid self-closing reaction with the adsorbed HDD on the substrate. All self-termination growth experiments were performed over 100 cycles. Saturation data indicate that DEZ and HDD are fully reactive with active sites on the surface and that the reaction does not persist after saturation, even in the presence of excess precursors.

The thickness of the ZnOPDA thin film as a function of MLD cycle number was measured using transmission electron microscopy (TEM) (FIG. 4A). TiO ₂ is added for color indication.

These TEM images confirmed the prediction of the monolayer thickness and MLD growth rate of the ZnOPDA film. Figure 4b shows that the polydiacetylenes thickness increases almost linearly with increasing number of cycles, indicating that the surface action in the MLD process is complementary and complete. The measured growth rate is about 5.2 Å per cycle, which is consistent with the ellipsometer results. The TEM image also showed that the ZnOPDA film was amorphous and had no ZnO nanocrystals. The AFM image of the ZnOPDA film showed a very smooth and uniform surface, and the root mean square (RMS) roughness of the surface was as low as 2.5 Å (FIG. 4c). This is compared to the initial cleaned Si substrate having a surface roughness of about 2.1 Å. Regardless of the number of cycles, the surface of the ZnOPDA film is as smooth as the initially cleaned Si substrate, indicating that the MLD growth has grown in a 2D fashion through layer growth and is evenly doped across the substrate. These results suggest that the MLD of the 2D polydiacetylenes is self-limiting and progresses by layer growth, and that the MLD conditions are sufficient for a complete reaction at temperatures of about 100 ° C to about 150 ° C.

The temperature stability of the ZnOPDA film was confirmed using a TEM. The ZnOPDA film was stable in air up to a temperature of about 400 ° C. These results confirm that the stability of 2D polydiacetylenes survived the TEM process and that the polydiacetylenes are covalently bound by the zinc oxide crosslinked layer.

Surface-enhanced Raman scattering (SERS) spectroscopy was performed to confirm the photopolymerization of the diacetylene thin film. A 100 nm thick Ag film was deposited on the Si (100) substrate using a vacuum evaporator. A 2-nm thick 2D polydiacetylene film was grown on the Ag film. Ag nanoparticles with a diameter of 60 nm were dripped onto the polydiacetylene surface under ambient conditions. 5A is a representative SERS spectrum of a ZnOPDA film placed between Ag nanoparticles and an Ag film. Three Raman bands were evident at ν ₁ = 2127 cm ^-1 , ν ₂ = 1525 cm ^-1 , and ν ₃ = 1060 cm ^-1 , which was in agreement with the Raman data already observed for the polydiethylene monolayer Respectively. The narrow band at 2917 cm ^-1 is due to CH oscillation. The remarkable and broad band around 1590 and 1360 cm ^-1 is similar to that observed by irradiation of the excitation laser, which is interpreted as a result of conversion from polydiacetylene to carbon material including graphite, amorphous carbon. The SERS results indicate that the diacetylene molecules of the film have been polymerized by UV irradiation, consistent with the commonly known photopolymerization of diacetylene.

X-ray photoelectron (XP) spectroscopy studies were conducted to determine the composition of the ZnOPDA thin films grown by the MLD process. 5B shows the irradiation spectrum of a 100 nm thick poly-diacetylene thin film grown on an Si substrate. The XP spectrum shows only photoelectron and Auger electron peaks for zinc, oxygen and carbon. The peak area ratio for these elements is 1: 3.2: 5.8 (Zn: O: C), which is corrected by the element sensitivity factor. For comparison, the expected ratio of the model structure of 2D polydiacetylenes (FIG. 1) was 1: 2: 6. Thus, it was confirmed that the ratio of Zn: O: C of 1: 3.2: 5.8 of this invention is very similar to the ideal Zn: O: C ratio. The higher percentage of oxygen atoms can be explained by the adsorption of H ₂ O to the ZnOPDA film. Water is mostly present on the surface of the film because the O1s peak is significantly reduced after the Ar ion sputtering compared to other peaks.

The photoluminescence (PL) spectrum of the ZnOPDA thin film is as shown in FIG. For the PL spectrum, a 100 nm thick polydiacetylene film deposited on a Si substrate was irradiated with a He-Cd laser (? = 325 nm) as an excitation source. 6, a broad peak around 500 nm was confirmed. PL spectra show the possibility of using ZnOPDA films in optical devices including electroluminescence. For comparison, a polydiacetylene (PDA) thin film without an inorganic cross-linking layer was also prepared by adding a methanol solution of 2,4-hexadiyne-1,6-diol (HDD) . A 6 mM HDD dissolved in methanol was spin-coated on the Si substrate for 1 minute at 1000 rpm and the substrate was exposed to UV light for 10 minutes to form a 100 nm thick PDA film. As a result, the spectrum of the prepared film was very similar to ZnOPDA but slightly shifted toward longer wavelength (FIG. 6). As described above, it was confirmed that the ZnOPDA film produced by the organic-inorganic hybrid thin film manufacturing method of the present invention shows photoluminescence results almost similar to that of the poly-diacetylene.

In order to investigate the electrical properties of the 2D polydiacetylene thin film, a thin film transistor (TFT) was fabricated by applying a ZnOPDA film as an active layer. The TFT has a ZnO-PDA semiconductor channel grown on a 100 nm thick SiO2 / n ⁺ -Si substrate at 100 DEG C, as can be seen in the device shown in Fig. The patterned Al source / drain electrode was vacuum-deposited on a ZnOPDA film using a shadow mask. As can be seen from Fig. 8, a typical output (drain current vs. drain voltage: I _D - V _D ) curve was obtained from a ZnOPDA TFT. The data indicate that ZnOPDA acts as an n-type semiconductor. The maximum I _D level was about 40 μA under a 100 V gate bias. According to the transition characteristics ( I _D - V _G ) seen in FIG. 9, a high field effect electron mobility of 1.3 cm ² V ^-1 s or higher has an on / off ratio of 10 ⁶ or more and a threshold voltage of 45 V, _Lt ; RTI _ID = 0.0 &gt; V _D = 100 V &lt; / RTI &gt; The gate leakage current ( I _G ) was less than 10 ^-10 A. The electron mobility is the highest among the polydiacetylene-based TFTs. Such a ZnOPDA TFT can increase the operating speed of a flexible electronic device. TFTs with 30 nm thick PDAs without cross-linking layers were fabricated, which showed significantly lower field-effect mobility (<10 ^-8 cm ² V ^-1 s) than ZnOPDA films.

As a result, a two-dimensional polydiacetylene having an inorganic crosslinked layer was developed using MLD. The MLD process enables precise control of film thickness at low temperatures, large uniformity, excellent conformality, excellent reproducibility and a sharp interface. The prepared ZnOPDA films exhibited excellent thermal stability, mechanical stability, and high field effect mobility (> 1.3 cm ² V ^-1 s). The MLD method is an ideal technique for the production of various 2D organic polymer thin films having an inorganic crosslinked layer, and is also applicable to the production of organic polymer-inorganic hybrid superlattices.

Experimental Example  2

Example  2 of TiOPDA  Investigate the characteristics of the film

IR spectra were obtained on an FTIR spectrometer (FTLA 2000). The spectrum was 64 scans at ¹ cm ^-1 intervals. KBr powder (Sigma Aldrich) was finely ground using a mullet and a mortar, and KBr pellets were prepared using a compactor. Al ₂ O ₃ was deposited using ALD technology to make a hydroxyl site on the pellet surface, and TiOPDA was prepared in the same manner as in Example 2. A UV-VIS spectrum of the TiOPDA film prepared as in Example 2 above was obtained on a Quartz plate (JMC glass) using a UV-VIS spectrometer (Agilent 8453 UV-Vis). All XP spectra were recorded on a VG Scientific ESCALAB MK II spectrometer using a MgKa source operating at 15 kV and 70 W. The binding energy scale was adjusted to 284.5 eV at the major C 1s peak. Each sample was analyzed at &lt; RTI ID = 0.0 &gt; 90 &lt; / RTI &gt;

result

FTIR spectroscopy was used to identify functional groups of TiOPDA thin films. Figure 10 shows the spectrum of the TiOPDA thin film produced. PDA IR spectra were also analyzed for comparison. Peaks at 1000 cm ^-1 and 1350 cm ^-1 indicate peaks of CO and CH ₂ bonds, respectively. A peak at 1600 cm &lt; ^-1 &gt; indicates that the diacetylene was polymerized via UV irradiation with a peak for C = C stretching.

UV-VIS spectroscopy was used to evaluate the optical properties of TiOPDA. 11 is a 50 nm thick TiOPDA UV-VIS spectrum grown on a Quartz plate. Compared with diacetylene, TiOPDA exhibited absorption peaks in the wavelength range of 300 nm to 400 nm.

X-ray photoelectron (XP) spectroscopy studies were performed to determine the composition of the TiOPDA thin films grown by the MLD procedure. 12 shows the irradiation spectrum of a TiOPDA thin film of 100 nm thickness grown on an Si substrate. The XP spectrum showed only photoelectron and Auger electron peaks for titanium, oxygen and carbon. The peak area ratio for these elements is 1: 5.6: 11.7 (Ti: O: C), which is corrected by the element sensitivity factor. For comparison, the expected ratio of the model structure of 2D polydiacetylenes (FIG. 2) was 1: 4: 12. Thus, it was confirmed that the ratio of Ti: O: C of 1: 5.6: 11.7 is very similar to the ideal Ti: O: C ratio. The C1s peak at 284.5 eV represents the conjugated carbon and the peak at 286 and 288.6 eV is the peak of the carbon bound to oxygen.

It will be understood by those of ordinary skill in the art that the foregoing description of the embodiments is for illustrative purposes and that those skilled in the art can easily modify the invention without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be interpreted as being included in the scope of the present invention .

Claims (15)

Organic-inorganic hybridization comprising interlayer bonding of a photopolymerizable organic polymer comprising polydiacetylenes or vinyl ether-alleimides polymerized by UV treatment to an inorganic crosslinking layer via molecular layer deposition (MLD) A method for producing a thin film. The method according to claim 1,
Bonding an inorganic crosslinked layer on a substrate in a molecular layer deposition chamber; And
Bonding the hexagonal diol (HDD) to the inorganic crosslinked layer bonded on the substrate and then polymerizing by UV treatment
Wherein the organic-inorganic hybrid thin film comprises at least one organic compound. delete The method according to claim 1,
Wherein the inorganic cross-linked layer comprises an oxide of a metal selected from the group consisting of Zn, Al, Ti, Zr, Sn, Mn, Fe, Ni, Mo and combinations thereof. . The method according to claim 1,
Wherein the organic-inorganic hybrid thin film is two-dimensional. 3. The method of claim 2,
Wherein the hexadienediol (HDD) is subjected to a self-terminating reaction when bound to the inorganic crosslinked layer bonded on the substrate. 3. The method of claim 2,
Wherein the inorganic cross-linked layer is bonded to the substrate, followed by purging the organic cross-linked inorganic thin film. 3. The method of claim 2,
Bonding the hexagayediol (HDD) to the inorganic crosslinked layer bonded to the substrate and then purifying the organic crosslinked thin film. 8. The method of claim 7,
Wherein the purging is purged with a purge gas containing argon (Ar), nitrogen (N ₂ ), or helium (He). 9. The method of claim 8,
Wherein the purging is purged with a purge gas containing argon (Ar), nitrogen (N ₂ ), or helium (He). An organic-inorganic hybrid thin film produced by the method for producing an organic-inorganic hybrid thin film according to any one of claims 1, 2, and 4 to 10. 12. The method of claim 11,
Wherein the organic-inorganic hybrid thin film is two-dimensional. An organic electronic device comprising the organic-inorganic hybrid thin film of claim 11. materials;
A semiconductor channel comprising the organic-inorganic hybrid thin film according to claim 11 formed on the substrate; And
A source / drain electrode
And a thin film transistor. 15. The method of claim 14,
Wherein the thin film transistor has a field effect mobility of 1.2 cm &lt; ² &gt; V &lt; ^-1 &gt; s or more.

Images